Classifications

• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/075—Silicon-containing compounds
  • G03F7/0757—Macromolecular compounds containing Si-O, Si-C or Si-N bonds
• • G—PHYSICS
  • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
  • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
  • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
  • G03F7/004—Photosensitive materials
  • G03F7/022—Quinonediazides
  • G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders

Definitions

• the present invention relates to a silicone resin/phenolic resin hybrid compound in which a silicone resin component is dispersed within a phenolic resin at a molecular level and the silicone resin component and phenolic resin are interlocked in a network-like manner.
• the invention also relates to a resist containing the hybrid compound, and to a patterning process which uses the resist.
• novolac resin-containing organic-inorganic polymer hybrids as resists and a method for the preparation of such hybrids are described in JP-A 2000-44876 and JP-A 2000-56453. Resists of this type purportedly enhance the heat resistance of the resist film, making it less subject to deformation, and also improve the dry etching resistance of the film.
• the substrate to which the resist is applied generally is a silicon wafer. Lately, however, a variety of applications are being proposed which call for the use of resists on not only silicon substrates, but also metal substrates such as copper, gold, aluminum, chromium, titanium and tantalum substrates.
• the resist film must have the ability to adhere to such metal substrates.
• Methods for improving adhesion of the resist to the substrate include, in particular, the incorporation of an additive, such as that obtained by adding an organic hydroperoxide to an N-substituted imide (JP-B 48-3616), the addition of an aminoalkoxysilane (JP-A 51-52002), the addition of a chelate complex-forming hydroxyl group-bearing aromatic or aliphatic compound (JP-A 52-54503), and the addition of a silane coupling agent (JP-A 53-39115).
• an additive such as that obtained by adding an organic hydroperoxide to an N-substituted imide (JP-B 48-3616), the addition of an aminoalkoxysilane (JP-A 51-52002), the addition of a chelate complex-forming hydroxyl group-bearing aromatic or aliphatic compound (JP-A 52-54503), and the addition of a silane coupling agent (JP-A 53-39115).
• the invention provides a hybrid compound which includes a phenolic resin and a silicone resin prepared by the hydrolysis and condensation of an organooxysilane of the general formula (1):
• R 1 is a sulfur- or oxygen-bearing monovalent hydrocarbon group
• R 2 represents a monovalent hydrocarbon group
• n is 1 or 2.
• the phenolic resin is preferably a novolac resin comprising recurring units of the general formula (2):
• m is an integer from 0 to 3, which has a polystyrene equivalent weight-average molecular weight of 1,000 to 10,000, and in which 1 to 50 mol % of the hydroxyl group hydrogens are substituted with 1,2-naphthoquinonediazido-sulfonyl ester groups.
• the invention also provides a resist comprising the foregoing hybrid compound.
• the invention further provides a patterning process which includes the steps of (i) applying the foregoing resist to a substrate, (ii) exposing the applied resist through a photomask to light having a wavelength of 150 to 450 nm, and (iii) developing the exposed resist with a liquid developer.
• the silicone resin/phenolic resin hybrid compound of the invention is a compound obtained by adding an organooxysilane of the general formula (1):
• the silicone resin derived from the organooxysilane is interlocked with the phenolic resin in a network-like manner.
• R 1 is a sulfur- or oxygen-bearing monovalent hydrocarbon group
• R 2 represents a monovalent hydrocarbon group
• the letter n is 1 or 2.
• sulfur-bearing monovalent hydrocarbon groups that may serve as R 1 include mercapto group-containing C 1-8 alkyls such as mercaptomethyl, mercaptoethyl, mercaptopropyl, mercaptobutyl, mercaptopentyl, mercaptohexyl, mercaptobutyl and mercaptooctyl; mercapto group-containing C 6-10 aryls such as mercaptophenyl and mercaptomethylphenyl; and mercapto group-containing C 7-12 aralkyls such as mercaptobenzyl, mercaptomethylbenzyl and 2-phenyl-1-mercaptoethyl.
• oxygen-bearing monovalent hydrocarbon groups that may serve as R 1 include glycidoxy or epoxy group-containing C 4-8 alkyls such as glycidoxymethyl, glycidoxyethyl, glycidoxypropyl, glycidoxybutyl, glycidoxypentyl and (3,4-epoxycyclohexyl)ethyl; and methacryloxy group-containing C 4-8 alkyls such as methacryloxymethyl, methacryloxyethyl, methacryloxypropyl and methacryloxybutyl.
• C 4-8 alkyls such as glycidoxymethyl, glycidoxyethyl, glycidoxypropyl, glycidoxybutyl, glycidoxypentyl and (3,4-epoxycyclohexyl)ethyl
• methacryloxy group-containing C 4-8 alkyls such as methacryloxymethyl, methacryloxyethyl
• Illustrative examples of the monovalent hydrocarbon groups represented in the above formula as R 2 include C 1-8 alkyls, C 6-10 aryls such as phenyl and tolyl, and C 7-12 aralkyls such as benzyl and phenylethyl.
• Phenolic resins that may be used in the invention include substituted or unsubstituted novolac resins and polyhydroxystyrene resins. Preferable use can be made of a novolac resin which has recurring units of the general formula (2):
• m is an integer from 0 to 3, which has a polystyrene equivalent weight-average molecular weight of 1,000 to 10,000, and in which 1 to 50 mol %, especially 3 to 30 mol % of the hydroxyl group hydrogens are substituted with 1,2-naphthoquinonediazidosulfonyl ester groups.
• the photosensitive groups are preferably, though not necessarily, naphthoquinonediazide groups.
• the silicone resin/phenolic resin hybrid compound of the invention can be prepared by the following method.
• a phenolic resin is dissolved in an alcohol having 1 to 8 carbons, such as methanol or ethanol.
• An organooxysilane component of above general formula (1) is added to the resulting solution, and a sol-gel reaction is carried out via hydrolysis and condensation in the presence of water.
• An acid such as hydrochloric acid or p-toluenesulfonic acid may be added as the catalyst, although acid addition is not always necessary because the hydroxyl groups on the phenolic resin are intrinsically acidic.
• the organooxysilane of above formula (1) is used in an amount of preferably 1 to 60 wt %, and most preferably 3 to 50 wt %, based on the phenolic resin.
• organooxysilane At less than 1 wt % of the organooxysilane, it may be impossible to achieve the object of the invention. On the other hand, an organooxysilane content of more than 60 wt % may greatly compromise the uniformity of application and the resolution of the resist.
• the sol-gel reaction may be carried out by an ordinary method for the hydrolysis and condensation of organooxysilane, although reaction at a temperature of 20 to 80° C., and especially 30 to 60° C., for a period of 0.5 to 5 hours, and especially 1 to 3 hours, is preferred.
• the product can be used as a resist component once the alcohol that has formed in the reaction and excess water have been removed by distillation.
• Such removal of alcohol and water is preferably carried out by vacuum distillation at a temperature of less than 40° C. If the organooxysilane contains photosensitive substituents such as naphthoquinonediazide groups, raising the temperature too high may lead to decomposition of the naphthoquinonediazide groups, resulting in a loss of the desired characteristics in resists containing the hybrid compound.
• the silicone resin/phenolic resin hybrid compound of the invention can be used as a resist.
• the hybrid compound it is preferable for the hybrid compound to be present in an amount of 1 to 60 wt %, and especially 3 to 50 wt %, of the resist solids other than the hybrid compound.
• the presence of less than 1 wt % may prevent the objects of the invention from being achieved, whereas more than 60 wt % may have a very detrimental effect on the uniformity of application and the resolution of the resist.
• Resists containing this silicone resin/phenolic resin hybrid compound may also include a photosensitizer.
• the photosensitizer used for this purpose is preferably a 1,2-quinonediazide compound, illustrative, non-limiting examples of which include 1,2-naphthoquinonediazido-4-sulfonic acid esters and 1,2-naphthoquinonediazido-5-sulfonic acid esters.
• the amount of photosensitizer included in the resist is preferably 5 to 50 parts by weight, and most preferably 10 to 40 parts by weight, per 100 parts by weight of the silicone resin/phenolic resin hybrid compound.
• the resist is typically used as a solution in an organic solvent. Any organic solvent in which the resist is fully soluble and which confers a good film-forming ability may be used for this purpose.
• suitable organic solvents include cellosolve solvents such as methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate and ethyl cellosolve acetate; propylene glycol solvents such as propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol dimethyl ether and propylene glycol monoethyl ether acetate; ester solvents such as butyl acetate, amyl acetate, methyl lactate, ethyl lactate, ethyl 3-methoxypropionate and ethyl 3-ethoxypropionate; alcohol solvents such as hexanol and diacetone alcohol; ketone solvents such as cyclohexanone and methyl amyl ketone; ether solvents such as methyl phenyl ether and diethylene glycol dimethyl ether; highly polar solvents such
• the resist of the invention may include also such additives as leveling agents, various types of surfactants, and dyes.
• a known lithographic process may be used to pattern the resist of the invention.
• the resist is typically spin-coated or otherwise applied to a substrate such as a silicon wafer, then pre-exposure baked on a hot plate at 60 to 150° C. for 1 to 10 minutes, and preferably at 80 to 120° C. for 1 to 5 minutes, so as to give a resist film having a thickness of 0.5 to 2.0 ⁇ m.
• the resist film is exposed, through a patterning mask held over it, to about 1 to 200 mJ/cm 2 , and preferably about 1 to 100 mJ/cm 2 , of sub-500 nm wavelength high-energy radiation or electron beams. If necessary, the resist film is then post-exposure baked on a hot plate at 60 to 150° C. for 1 to 10 minutes, and preferably at 80 to 120° C. for 1 to 5 minutes.
• the exposed resist is then developed by an ordinary method, such as a dip, paddle or spray process, for a period of 0.1 to 3 minutes, and preferably 0.5 to 2 minutes, using an aqueous alkali solution such as 0.1 to 5 wt %, and preferably 2 to 3 wt %, tetramethylammonium hydroxide (TMAH), thereby forming the desired pattern on the substrate.
• an aqueous alkali solution such as 0.1 to 5 wt %, and preferably 2 to 3 wt %, tetramethylammonium hydroxide (TMAH)
• a three-necked flask equipped with a stirrer, a condenser and a thermometer was charged with 59.5 g (0.55 mol) of p-cresol, 48.7 g (0.45 mol) of m-cresol, 48.7 g (0.52 mol) of a 37 wt % formaldehyde solution in water, and 0.30 g (2.40 ⁇ 10 ⁇ 3 mol) of the polycondensation catalyst oxalic acid dehydrate.
• the flask was then immersed in an oil bath and polycondensation carried out for one hour while maintaining the internal temperature at 100° C.
• MIBK methyl isobutyl ketone
• reaction mixture was aged for one hour, then poured into 5,000 ml of 0.1 N hydrochloric acid in water.
• the precipitate that formed was collected by filtration and dissolved in 800 g of methyl isobutyl ketone, after which the solution was washed with water and the water discarded.
• Vacuum stripping at 40° C. yielded 142 g of a novolac resin B in which 10 mol % of the hydroxyl group hydrogens on the original novolac resin A were substituted with 1,2-naphthoquinonedizidosulfonyl ester groups.
• the product was dissolved, together with 0.01 g of the surfactant X-70-093 (trade name, produced by Shin-Etsu Chemical Co., Ltd.), in 5 g of propylene glycol monomethyl ether acetate.
• the resulting solution was passed through a membrane filter having a pore size of 0.2 ⁇ m, giving 10 g of a resist A composed primarily of a silicone resin/novolac resin hybrid compound.
• Resist A was applied with a spinner to a substrate composed of a 6-inch bare silicon wafer onto which chromium had been sputtered, and the resist-coated substrate was pre-baked on a hot plate at 100° C. for 120 seconds to form a 6.0 ⁇ m thick resist film.
• Example 2 the product was dissolved, together with 0.01 g of the surfactant X-70-093, in 5 g of propylene glycol monomethyl ether acetate. The resulting solution was passed through a membrane filter having a pore size of 0.2 ⁇ m, giving 10 g of a resist B composed primarily of a silicone resin/novolac resin hybrid compound. Resist B was then spun onto a substrate composed of a 6-inch bare silicon wafer onto which tantalum had been sputtered. Adhesion of the resulting resist film to the substrate was rated in the same way as in Example 1.
• Example 2 the product was dissolved, together with 0.01 g of the surfactant X-70-093, in 5 g of propylene glycol monomethyl ether acetate. The resulting solution was passed through a membrane filter having a pore size of 0.2 ⁇ m, giving 10 g of a resist C composed primarily of a silicone resin/novolac resin hybrid compound. Resist C was then spun onto a substrate composed of a 6-inch bare silicon wafer onto which gold had been sputtered. Adhesion of the resulting resist film to the substrate was rated in the same way as in Example 1.
• Example 2 the product was dissolved, together with 0.01 g of the surfactant X-70-093 and 1.5 g of the photosensitizer P of above general formula (3), in 5 g of propylene glycol monomethyl ether acetate. The resulting solution was passed through a membrane filter having a pore size of 0.2 ⁇ m, giving 10 g of a resist E composed primarily of a silicone resin/novolac resin hybrid compound. Resist E was then spun onto a substrate composed of a 6-inch bare silicon wafer onto which tantalum had been sputtered. Adhesion of the resulting resist film to the substrate was rated in the same way as in Example 1.
• Example 2 the product was dissolved, together with 0.01 g of the surfactant X-70-093, in 5 g of propylene glycol monomethyl ether acetate. The resulting solution was passed through a membrane filter having a pore size of 0.2 ⁇ m, giving 10 g of a resist F composed primarily of a silicone resin/novolac resin hybrid compound. Resist F was then spun onto a substrate composed of a 6-inch bare silicon wafer onto which gold had been sputtered. Adhesion of the resulting resist film to the substrate was rated in the same way as in Example 1.
• Example 2 the product was dissolved, together with 0.01 g of the surfactant X-70-093, in 5 g of propylene glycol monomethyl ether acetate. The resulting solution was passed through a membrane filter having a pore size of 0.2 ⁇ m, giving 10 g of a resist G composed primarily of a silicone resin/novolac resin hybrid compound. Resist G was then spun onto a substrate composed of a 6-inch bare silicon wafer onto which chromium had been sputtered. Adhesion of the resulting resist film to the substrate was rated in the same way as in Example 1.
• Example 2 the product was dissolved, together with 0.01 g of the surfactant X-70-093, in 5 g of propylene glycol monomethyl ether acetate. The resulting solution was passed through a membrane filter having a pore size of 0.2 ⁇ m, giving 10 g of a resist H composed primarily of a silicone resin/novolac resin hybrid compound. Resist H was then spun onto a substrate composed of a 6-inch bare silicon wafer onto which tantalum had been sputtered. Adhesion of the resulting resist film to the substrate was rated in the same way as in Example 1.
• Example 1 Silicone resin/ novolac Substrate hybrid surface Adhesion compound Organooxysilane metal (1.5 ⁇ m l/s)
• Example 1 A ⁇ -glycidoxypropyltriethoxysilane chromium no pattern flow
• Example 2 B ⁇ -methacryloxypropyltrimethoxysilane tantalum no pattern flow
• Example 3 C ⁇ -mercaptopropyltrimethoxysilane gold no pattern flow
• Example 4 D ⁇ -glycidoxypropyltriethoxysilane chromium no pattern flow
• Example 5 E ⁇ -methacryloxypropyltrimethoxysilane tantalum no pattern flow
• Example 6 F ⁇ -mercaptopropyltrimethoxysilane gold no pattern flow Comparative G phenyltriethoxysilane chromium some Example 1 pattern flow Comparative H phenyltriethoxysilane tantalum some Example 2 pattern flow
• the invention provides hybrid compounds which, when used as the base polymer in a resist, confer a film of the resist formed on a metal substrate with excellent adhesion to the substrate.

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• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• General Physics & Mathematics (AREA)
• Materials For Photolithography (AREA)
• Phenolic Resins Or Amino Resins (AREA)
• Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Silicon Polymers (AREA)

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Citations (10)

• 2001
  • 2001-10-12 JP JP2001314863A patent/JP2003119344A/ja active Pending
• 2002
  • 2002-10-11 US US10/268,761 patent/US6790581B2/en not_active Expired - Fee Related

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